Process of producing aqueous dispersions of water immiscible bodies



Patented Nov. 24:, 3933.

near var es TNT- err-- W BEACH PH, OH W'ELLESLEY, MASSACHUSETTS, ASSIGNOE, BY MERE ASSIGNMENTS, T DISPESIONS PROCESS, INC., 01 D0, DWE, A CORPQ- BATION 0F DELAWARE IPRGCESS OEERODUCIN G AQUEQUS DISPERSIONS OF WATER IMMISLE B01) 5 No Drawing.

I have discovered that it is possible to produce aqueous dispersions of bodies or substances, many of which have heretofore re-I sisted efforts so to disperse them and have 1 been regarded as impossible of aqueous dispersion. Among such bodies, as may be dispersed in water by the process which I shall hereinafter set forth, are crude rubber, balata, gutta percha, noncolloidal sulphur-terpenes, natural and synthetic resins, vegetable and mineral waxes, gums, tars, pitches, bitumens, animal and vegetable oils, etc, which are soluble in nonaqueous solvents.

This is accomplished by the employment of a colloid, which, in the examples hereinafter described takes the form of asoap. The col I loid is caused to be disseminated through the mass to be dispersed, and forms protective films or coatings for the dispersed particles. m In the examples which I have hereinafter described, the soap may be formed insitu by first disseminating through the mass a saponifiable substance and then incorporating a saponifying agent. The addition of 25 water to the mass, which in the examples hereinafter given is partly coincident with the addition of thb saponifying agent, finally results in the dispersion of the water-insoluble body in the aqueous medium. The mass 39 to be dispersed may be conditioned for dispersibn, by the employment of a suitable solvent, which is abstracted from the final product'after the dispersion is effected. I 235 have hereinafter described in detail a process, constituting one mode of practicing the invention, by which, such .water-insoluble bodieshereinbefore referred to may be dis persed in water.

v Stated briefly, such process consists first in t dissolving the substance to be dispersed in a suitable solvent,.and then replacing the solvent in whole or in part with water, withoutthrowing down, precipitating or coagulating a the dissolved substance but leaving it as the disperse phase in the continuous aqueous phase. In accomplishing this result, it is necessary, when the substance to be dispersed does not of itself contain or have as a component thereof a dispersing agent, to add or to form situ a dispersing colloidal fippliatton filed October 17, 1922. Serial No. 595,213.

agent, preferably in the form of an ammomum soap. In many cases, where the agent is to be formed in situ in the solution of the body to be dispersed a saponifiable substance is dissolved in the solution, and to the water, in which the body is to be dispersed is added the saponifying matter; so that, when'the water is mixed into the "solution,- the said substance is saponified and acts as the dispersing agent, being in such case difi'used ,or dispersed throughout the mass. In using the term saponify, I do not mean to ,imply that. the substance is necessarily hydrolyzed (-though this may indeed take place), as'I employ the term in the broader sense that the saponifiable substance may form a soap. Thus as the saponifiable substance I may use either oleic acid or a suitable liquid glyceride or mixture of glycerides such as a vegetable' oil.

Care must be exercised in the selection of the solvent for the body to be dispersed. In some cases the alcohols may be employed, whereas in others benzol, toluol, xylol or other solvents of the aromatic or carbocyclic series should be employed. The character of the soap which is utilized as the dispersing agent for stabilizing the dispersion depends to some extent upon the character of the body tobe dispersed, but inmost cases ammonium oleate is the most satisfactory, although of course it will be understood that the process is not necessarily limitedto the use thereof. Certain metallicsoaps have the efiect of coagulating or throwing down.some of the dispersed bodies and their use should be avoided where such bodies are employed. In fact, so far as my work has progressed, ammonla soap appears to be the only soap which should be used as a dispersing agent in forming an aqueous dispersion ofriibber, balata or gutta percha, when it isldesired to form the soap in situ in the rubber solution, since the saponification may be accomplished at a relatively low temperature at which coagulation of the disperse phase of the dispersion is avoided.

I herein set forth certain typical examples of the mode of carrying out my process and producing aqueous dispersions of bodies which are immiscible withor insoluble in Ell water, but it will be understood that the invention is in no wise l-imited thereto.

Example I.For the production of an aqueous crude rubber dispersion, I proceed as follows: In 750 grammes of benzene (or commercial benzol), dissolve 250 grammes of crude rubber (balata or gutta percha) and grammes of oleic acid, with proper a itation until the oleic acid is diffused throng out the mass. Thoroughly mix 20 grammes of 26 aqua ammonia with 7 5O grammes of water. Then add and thoroughly mix the water with the rubber solution. The dis persed or difi'used particles of oleic acid are saponified by the ammonia in situ,-forming an ammonia sea which acts as a dispersing agent and stabilizes the final dispersion. 11s the ammoniated water is added to and stirred in the rubber-benzol solution, it will be observed that at first the water forms the disperse phase of the dispersion, but, as the total volume otwater increases, there is a change of phase, and the water then constitutes the continuous phase. The final dispersion is a white milky mass which may be diluted practically to any reasonable or operative extent with water. It may be used as thus produced, but, if desired, the solvent may be .re-

moved by evaporation, but preferably in a vacuum still at a low temperature (say, not over C.) for recovery of the solvent. The dispersed rubber niay be easily coagulated by the common materials employed for coagulating crude rubber and the rubber thus co.- agulated has the characteristics of the rubber prior to its dispersion. It may be vulcanized with the same sulphur factor and heat coeificient as the original crude rubber.

Example ll.-To produce an aqueous dispersion of parafin, noncolloidal sulphur-ter pene (such as commercially termed Toron), or other body soluble in benzol, toluol, xylol or the like,0ne may substitute either for an equivalent amount of rubber and proceed as in Example ll.

Example III-A dispersion of two or I more difierent bodies, such as rubber, parafin and resin, may be secured by dissolving the bodies in the same solvent,benzol for ex-' ample,-together. with oleic acid, and then mlxing with the solution an amount of water, equal to the benzol, to which was added ammonia in excess of that required to saponify the oleic acid, as given in Example I.

Ea2ample [V.-Those bodies which are sol uble in alcohol may be dissolved therein, fol-' lowing substantially the procedure outlined" 111 Example I, but substituting alcohol for.

the benzene ole/other solvent of the aromatic or carbocylic se1 ies. Thus 250 grammes gum sandarac together with 25 grammes of oleic acid may be dissolved in 750 grammes of ethyl alcohol, and 750 grammes of water With 20 grammes of 26 aqua ammonia gradually mixed therewith, and an apparently clear liquid produced, from which the alcohol may be evaporated. The aqueous dispersion thus produced may be mixed with those dispersions roduced by the utilization of other solvents or the dispersed bodies.

I regard it as more desirable to form the dispersing or stabilizing agent in situ, as it is thereby possible to secure a greater or more thorough difiusion of the particles of soap throughout the mass than when the soap is first formed and then added either to the water or to the solution; but, of course, in those cases Where for commercial or economical reasons it is expedient to employ an externally formed soap, 1 should not regard its use necessarily as a departure from the spirit of the invention. Again,-in certain cases, the body itself may contain saponifiable constituents, asin the case of some of the resins; and, in such event, the mere addition of a saponifying agent, such as ammonia, may be suflicient for the formation of a suflicient proportion of resin soap to act as a dispersing agent for the remainder of the resinous bodies, without the addition to the solution of oleicacid or other saponifiablc I agent.

In the examples hereinbefore given, as illustrative of various dispersions and the process of producing them, it Will be noted that a small proportion of soap to the dispersible body is employed, and also that the ammonia is in excess of that required for the saponification of the oleic acid. Approximately 10% or less of oleic acid (by weight) to the dispersible body is sufficient to furnish, with the requisite amount of am- IUU monia, enough soap for the most minute subdivision and dispersion of the body throughout the continuous aqueous phase. In the case of rubber dispersion, the dispersed particles are globular, and in size approxiindafte and in many cases are no larger than the rubber globules in rubber latex. Since ammonium oleate: is unstable and easily breaks down, it is quite likely that the excess ammonia serves to prevent such breaking down. While I am able to produce dispersions. by a process wherein the ammonia is in amount just sufiicient to saponify the oleic acid, yet the dispersion of the dispersedbody is not so fine as when the ammonia is in excess. The particles are of such order of minuteness, as topermit of the development of the Brownian movement.

. When any of these aqueous dispersions are formed, the disperse phase thereof may be coagulated or precipitated from the continuous phase by the use of a suitable agent I such as acetic or other acid, or alum, or other substance commonly employed for coagulatingrubber from the latex, or by the use ofheat or continued stirring,.as the case may be.

Such aqueous dispersions as herein described may be employed in the manufacture aeaaose of all kinds offelted fabrics, as for example in the production of felt for hat bodies, shoe stifi'eners, slippers, etc., or irrthe manufacture of paper, cardboard, box board, sheathing or roofing paper or felt, leather-board,the character of the dispersed body'depending upon the characteristics which the manufactured article should possess. Thus in the manufacture of a tough water-repellent paper, which may be flexed without breaking and which is torn with difiiculty, both crude rubber and paraifin or other suitable water-repelling body) are dispersed as herein set forth; and, after the fibrous stock has been beaten in the usual beating engine to the desired extent, the beater roll is lifted from the bed plate, and sufiicient dispersion (say, 2.5% of the dispersed bodies to 100% by weight of dry fiber) is added to the beater c0ntent and the operation of the roll continued until the dispersion is thoroughly incorporated in the fibrous mass. In the case of rubber, the agitation is ordinarily sulficient to effect the coagulation of the'rubber particles which adhere to the fibers, but it is at times desirable to add a precipitating or coagulating agent. The water runs clear with little or no waste of the precipitated or coagulated size. The pulp is then sheeted on any suitable paper machine, either in a continuous web or in a tube on the make-up roll of a wet machine. In the event that a web is formed by a multi-cylinder machine, the top or bottom (or both) laminations of the sheet may be formed of any usual paper stock, and one or more intermediate layers may be formed of the rubberized 0r paraffined or other sized stock, or these conditions may be reversed and only the outer layers or laminations (on one face or both) of the sheet be formed'of-the sized stock. Where the dispersed body is capable of coalescence under heat(e. g. pitches, bitumen, resins, waxes, gums), the sheet may be heated (and pressed, if desired) sufiiciently after its formation to effect such coalescence. It will be seen from the foregoing that papers or felted sheets having the desired physical characteristics, may be produced by the use of-a suitable aqueous dispersion incorporated in the pulp prior to the formation of the sheet.

Coated or treated webs or fabrics may be produced by passing previously formed slfeets through an aqueous dispersion of the To assist 'in the penetration of the body into the fabric, it is desirable i some instances not to efiect the evaporatidii of the solvent in which such body was-previously dissolved. Thus in the case of the so-called Toron (a noncolloidal sulphur-terpene), a cotton tire fabric or cord may be prepared bypassing it through an aqueous dispersion of such sulphur-terpene from. which the benzol hasnot, been re- .moved,the subsequent drying of the fabric efi'ectin the evaporation of the solvent. In ot er cases, however, the solvent may be recovered from the dispersion prior to the treatment of the fabric with the latter, thereby obviating the necessity of a recovery apparatus in the fabric-treating plant.

In the manufacture of leather board or soles for footwear, one may incorporate in the pulped scrap leather a rubber dispersion together with suitable compounding materials, and form the pulped mass into sheets either by use of a paper machine or by rolling it out. In this, as in other cases, where the product may be subjected to vulcanization, there may be dissolved in the benzol or other equivalent solvent a certain amount of sulphur (sufiicient to effect the vulcanization of the rubber), together with the rubber-and oleic acid, before adding the ammoniated water. Then, when the sheet is formed of the pulped fiber, and'is dried, the sheet may be subjected to a vulcanizing temperature (under pressure, if desired) to vulcanize the sheet. In lieu of pulped leather, one may utilize a pulp formed of various animal or vegetable fibers, or both, such as cattle hair, wood pulp, cotton rags, etc. I

. Aqueous dispersions of various bodies such as herein referred to may be utilized for various other purposes, depending upon the characteristics of the dispersed bodies. Thus they may be employed as shoe pastes, leather dressings, or floor and furniture polishes, or may be used for waxing threads or cords, or for sizing various materials.

In reference to the'use of solvents for the bodies to be dispersed, those hydrocarbon solvents, of the aliphatic or paraflin series such as produced from petroleum, e. g. benzin,

appear to be ineffective in producing a dispersion of certain of the bodies,--although, as I have already stated, certain bodies may be dissolved in alcohol prior to their dispersion in water. Of course, when the dispers ing agent is formed in situ, the body to be dispersed preferably should be soluble in the same solvent in which is dissolved the body "to be dispersed. But on the other hand as phurchloride is utilized, or a pr0cess in. whichl rydrogen sulphide and sulphur dioxide are used.-

While I have herein described the aqueous dispersion of crude' or coagulated rubber,

balata. and gutta-percha, which priginally occurs in nature dispersed in globular form in i i various lattices, ll do not herein specifically claim the process of dispersion of such congulated bodies or the products produced there by, since these form the subject-matter of my-application Serial No. 604,616, filed December 2, 1922. I

This is a continuation, so far as generic subject-matter is concerned, of my application Serial No. 583,903, filed August 23, 1922.

What I claim is 1. A process of dispersing in water water 7 insoluble bodies which are soluble in organic solvents, which comprises dissolving such a body, together with a saponifiable agent, in an organic solvent, incorporating in such. solution Water and a saponifying agent to produce a colloidal dispersing agent in situ in the mass, dispersing such solution with the aid 0f said dispersing agent in water, and by Vacuum distillation removing said solvent, thereby leaving said water-insoluble body dispersed in fine particle size in colloidal dispersing agent while maintain ing the solvent with the Water-immiscible body, and finally vacuum-distilling the solvent, thereby leaving said Water-immiscible body dispersed in fine particle size in the water.

4-. A process of dispersing in water waterimmiscible bodies which are soluble in organic solvents, which comprises dissolving such a body in said last-mentioned solvent, dispersing such solution with agitation in an aqueous medium in water containing a colloidal dispersing agent while maintaining the solvent with the water-immiscible body, and finally vacuum-distilling the solvent below 50 (3., thereby leaving said water-immiscible body in fine particle size in the 'Water.

In testimony whereof I have afifixed my signature.

WILLIAM BEACH PRATT.

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